<p indent=0mm>Due to highly rigid demanding for various functional photocatalysts in energy conversion and environmental applications, TiO<sub>2</sub> stands as one of the most widely studied semiconductors and highlighted for heterogeneous photocatalysts. By splitting water in solar energy conversion cells, it also serves as the promising candidate for photoanode material. The distinguished popularity of TiO<sub>2</sub> is attributed to many advantages, such as relatively high quantum efficiency, low cost, biocompatibility, and high optical and chemical stability. In recent years, controlling the structural parameters of TiO<sub>2</sub> is of particular importance which determines the efficiency and physicochemical properties of the resultant photocatalysts. However, two obvious shortcomings restrict the wide applications of TiO<sub>2</sub>. On the one hand, the rapid electron-hole recombination results in low quantum yield, which makes it more difficult to efficiently purify sewage in large scale and concentrated pollutants. On the other hand, due to its wide band gap <sc>(~3.2 eV),</sc> TiO<sub>2</sub> can only take effect in the UV region of the solar spectrum (~5% of the solar energy), while the energy absorption in the range of visible light containing about 45% of the solar energy cannot be captured. In order to extend the spectral range of the TiO<sub>2</sub> response, deposition of noble metals, such as Ag, on TiO<sub>2</sub> serves as one of the effective methods to reduce the chance of electron-hole recombination in photocatalytic process by coupling with the versatile properties of photocatalytic and antibactericidal activities. Ag could contribute to the formation of Schottky barriers at Ag/TiO<sub>2</sub> interfacial contact area, resulting in the reduction of electron-hole recombination in the photocatalytic process. Meanwhile, Ag brings in extra absorption bands at visible light spectra due to surface plasmon resonance (SPR) effect. The spectral range of the response of TiO<sub>2</sub> could be further extended to a much longer wavelength. However, it is found that the controllability of deposition of Ag on TiO<sub>2</sub> surface is weak in the process in regular methods, such as photodeposition, chemical reduction, and thermal impregnation, which usually require complicated equipment or toxic nitrogen for modification of TiO<sub>2</sub> with Ag. Hence, it is desired to explore a simple and nontoxic method to fabricate Ag/TiO<sub>2</sub> composite nanoparticles. Laser ablation is considered as a flexible method to synthesize nanoparticles, offering an alternative green route to well-separated nanoparticles. In this study, a simple, direct and flexible method by coupling pulsed laser ablation with hydrothermal treatment was used to obtain multiscale structured Ag/TiO<sub>2</sub> nanocomposites. Underwater laser ablation of metal targets has the characteristics of instantaneous high temperature and high pressure in heat affected zone due to confinement effect in aqueous condition, while the generated plasma quenched rapidly and formed rich nanostructures. Meanwhile, hydrothermal method shows great convenience for regulating the morphology of nanoparticles, smaller crystal thermal stress, smaller macro defects as well as higher uniformity. By optimizing the sequence of hybrid processing and hydrothermal reaction time, sea urchin structures and dendritic structures of TiO<sub>2</sub> were successfully prepared, enhancing the ultraviolet light absorption by scattering effect in the multiscale structures. Ag nanoparticles were further loaded on TiO<sub>2</sub>, avoiding the aggregation and obtaining Ag/TiO<sub>2</sub> composite materials with excellent optical properties. Spherical Ag particles around <sc>20 nm</sc> were dispersedly deposited on the burrs of sea urchin structured TiO<sub>2</sub>. Meanwhile, the secondary laser processing provides extra activation energy to further regulate TiO<sub>2</sub> morphology, leading to the formation of dendritic structures. Similar Ag nanoparticles were also successfully deposited or embedded on the surface of TiO<sub>2</sub> dendritic structures in the range of <sc>20–60 nm</sc> width. The crystallinity of as-prepared Ag-loaded TiO<sub>2</sub> is significantly improved by combing the rutile phase of TiO<sub>2</sub> with face-centered cubic structured Ag nanoparticles. The peak of TiO<sub>2</sub> light absorption will be red-shifted in the ultraviolet region and loaded Ag nanoparticles broadens the absorption band in the visible region. Wider absorption spectral band was achieved by Ag/TiO<sub>2</sub> composite with excellent optical properties, which can perform more application prospects in photocatalytic degradation of organic pollutants.